Halogenated octyl esters

ABSTRACT

The present invention relates to novel halogenated derivatives of esters of linear C8 alcohols and a process for the preparation of such compounds.

United States Patent Dobson June 17, 1975 HALOGENATED OCTYL ESTERS260/633 1 K 1 d E [75] nventor DgrannestliElzgl r211: Dobson, psomReferences Cited UNITED STATES PATENTS [73] Ass'gnee' gg r z lntemamna'2,865.953 12/1958 Nobis et al 260/491 [22] Filed: Aug. 13, 1973 QTHERPUB LICATIONS Groggms, Umt Processes m Org. Synthesis, p 212, [21]App1.No.: 387,951 (1952) QD 262 G7.

30 Foreign Application Priority Data j fi f"* -g g fiveinberger Aug. 25,1972 United Kingdom 39644/72 xammer am e y [52] US. Cl 260/475 R;252/546; 252/78; [57] ABSTRACT 260/31 8 260/469, 260/476 260/485 Thepresent 1nvent1on relates to novel halogenated derivatives of esters oflinear C alcohols and a process H 260/487, 260/488 F 260/491 260/652 R511 Im. c1. C07c 69/80 M PYePaatiO such [58] Field of Search 260/491,475 R, 475 N, 3 Claims, No Drawings HALOGENATED OCTYL ESTERS and x is Oor 1.

Specific examples of such compounds are di(2,3,7,8- tetrachloro-l-octyl)phthalate, 2,3,7,8-tetrachloro-1- octyl acetate,2,3,7,8-tetrachloro-l-octyl propionate and 2,3,7,8-tetrachloro-l-octylbenzoate.

The carboxylic acid moiety in the ester group is derived from asaturated aliphatic or an aromatic monoor di-carboxylic acid.

According to a further aspect of the present invention, a process forpreparing compounds of the formula (I) or (II) as hereinbefore definedcomprises reacting in the liquid phase an octodienyl ester with halogenat ambient temperatures.

The term halogen as used here and throughout the specification meanschlorine or bromine.

By the term linear C alcohols is meant throughout the specification thatthe carbon chain in the alcohol is linear. Thus the hydroxyl group ofthe alcohol could be in the lor 3- position of the carbon chain.

The octodienyl ester may suitably be prepared by reacting in the liquidphase butadiene with a carboxylic acid in the presence of a Group VIIImetal catalyst as described in British Patent Specification Ser. No.1,274,072. The techniques used for this stage should be well known to aperson skilled in the art.

The carboxylic acid moiety in the ester grouping is derived from asaturated aliphatic or an aromatic monoor di-carboxylic acid. Theseacids may contain in addition inert substituents, e.g. halogens or alkylgroups, in the aliphatic chain or in the nuclear positions of thearomatic carboxylic acids. Suitable examples of carboxylic acids whichmay be used include acetic, propionic, benzoic and phthalic acids.

The product from the above esteriflcation reaction is a mixture of land3- octadienyl monoor di-esters depending upon whether a monocarboxylicor a dicarboxylic acid is used for the reaction.

The mixture of land 3- octadienyl esters thus obtained may be used forthe halogenation step after separation from the catalyst solution byliquid/liquid extraction and removal of volatile olefins bydistillation. The halogenation is carried out in the liquid phase bydissolving the octadienyl esters in a solvent. The solvents used forthis purpose should preferably be more volatile than the esters and beinert to halogen, e.g. a halogenated hydrocarbon such as carbontetrachloride or chloroform. Basic solvents such as pyridine may also bepresent. The appropriate halogen gas, e.g. chlorine, is then passedthrough the solution of the octadienyl esters.

The halogenation may be carried out in the dark and- /or in the presenceof a free radical inhibitor such as tertiarty butyl catechol or oxygen.It may also be carried out in the presence of a Lewis acid such asferric chloride.

The halogenation step may be carried out at ambient temperatures. Byambient temperatures is meant temperatures below 60C, suitably below40C.

The halogenation step may be carried out at atmospheric,super-atmospheric or sub-atmospheric pressures.

The mixture of saturated halogenated derivatives thus obtained is thenrecovered by removal of the solvent and halogen by distillation underreduced pres sure, or by liquid/liquid extraction, drying and removingthe solvent by distillation.

The esters of linear Cg alcohols described here may be used asplasticizers in polymeric material such as PVC, as components oflubricants and in heat exchange fluids.

The invention is further illustrated with reference to the followingExamples:

EXAMPLE 1 Di( tetrachlorooctyl) phthalates Di(octadienyl) phthalates(113g), prepared by reaction of butadiene with phthalic acid in thepresence of a palladium catalyst, was dissolved in carbon tetrachloride(250 ml). The solution was cooled below 0C by means of an ice/salt bathand cooling coil, a slow stream of oxygen was passed through thesolution, and the glass reaction vessel was covered with aluminium foilto exclude light. Chlorine gas was passed into the solution at such arate that, with cooling, the temperature did not rise above 0C. The endof the reaction was signalled by a drop in temperature of the reactionsolution. The reaction solution was washed with aqueous sodiumthiosulphate solution, sodium carbonate solution, water, and dried overmagnesium sulphate. Removal of the carbon tetrachloride under reducedpressure gave di(tetrachlorooctyl) phthalates (197g) as a colourlessoil.

C H O CI requires: C, 43.2%; H, 4.50%; Cl 42.6%;

MW (molecular weight) 666. found: C, 41.0%; H, 4.3%; CI, 44.4%;

EXAMPLE 2 2,7-octadien-l-yl acetate (16.8g; 0.10 mole) was dissolved incarbon tetrachloride (100 ml) and the solution cooled below 0C by meansof a cooling coil. A slow stream of oxygen was passed through thesolution and the glass vessel covered with aluminium foil to excludelight. Chlorine was passed into the solution for 1.5h at such a rate ml.min) that, with cooling, the temperature did not rise above 0C. Thereaction solution was washed with an aqueous solution of sodiumsulphate/sodium bicarbonate, water (twice), and

dried over magnesium sulphate. The residue remaining after removal ofthe carbon tetrachloride under reduced pressure was steam stripped at70C for 15h and then vacuum stripped at 70C for 6h. The reaction product(23g) was analysed on a 1 feet X 741 inch silicone gum rubber onchromosorb W column. Three products were present in amount greater than5 area per cent on the gas liquid chromatograph chart. The productdistribution observed was:

GC Peak Compound A l ,2,3,7,8-pentachlorooctane 17 B l ,3,7,8-tetrachloro-2'octyl l9 acetate C 2.3.7.8-tetrachloro-l-octyl 39acetate D Several minor components 25 1,2,3 ,7 ,8-Pentachlorooctane PeakA was separated by solid liquid chromatography. Mass spectral analysiswas consistent with the formula C H Cl The nuclear magnetic resonancespectrum of l,2,3,7,8-pentachlorooctane in CDCl was as follows:

a b c d e f g h CH,ClCHCICH,CH,CH CHCICHClCH Cl 1'(tau) Area Habfgh5.4-6.7(m) 7H H c d e 7.5 8.8 (m) 6H C H CI requires: C, 33.

5%; H, 4.57%; Cl, 61.9% found: C, 33.6%; H, 4.3

l,3,7,8-tetrachloro-2-octyl acetate Peak B was separated by solid liquidchromatography followed by preparative gas liquid chromatography. Massspectral analysis was consistent with the formula C H O Cl The nuclearmagnetic resonance spectrum of l,3,7,8-tetrachloro-2-octyl acetateappeared as follows:

i OCOCH a b c d e f lg h CH ClCHClCH,CH,CH CHClCHCH,Cl

1' Area H 8 4.85 (m) 1H Habfh 5.66.6(m) 6H Hi 7.87 (S) 3H Hcde 7.9-8.8(m) 6H Proton decoupling at 8.22 1' resulted in no simplification of the4.85 multiplet.

C H O Cl requires: C, 38.7%; H, 5.20%; Cl, 45.7%; found: C, 37.3%; H,5.06%; CI, 47.7%

2,3,7,8-tetrachloro-1-octyl acetate Peak C was separated by solid liquidchromatography followed by preparative gas liquid chromatography. Massspectral analysis was consistent with the formula C H O Cl The nuclearmagnetic resonance spectrum of 2,3,7,8-tetrachloro-l-octyl acetate inCDCl was as follows:

a b c d e f g h i CH ClCHClCl-l CH CH CHClCHCICH,OCOCH;,

1 Area H h 5.5 (m) 2H Habfg 5.5-6.6(m) 5H H i 7.89 (s) 3H Hcde 7.7-88(m)6H C H O CL, requires: C, 38.7%; H, 5.20%; Cl, 45.7%; MW, 310; found: C,38.7%; H, 4.99%; Cl, 46.8%; Mol Wt 325 As can be seen from this Example,the process also results in the formation of the 2-ester besides theland- /or 3- esters.

EXAMPLE 3 l,7-Octadien-3-yl acetate (168g; 0.10 mole) in carbontetrachloride ml) was treated with chlorine as described in example 2except that the chlorine was passed at 50 ml min for 3h. The reactionproduct (26.4 g) was isolated and analysed by gas liquid chromatographyas described in Example 2. Three products were present in amountsgreater than 5 area percent:

GC Peak Compound A l,2,3,7,8-pentachlorooctane 3 3 Bl,2,7,8-tetrachloro-3octyl acetate 55 C unidentified l l i OCOCH;

a b c d e CH,ClCHClCH,CH,CH,CHCHClCH,Cl

f g h 1- Area H t 4.75 (m) 1H Habgh 5.6-6.7 (m) 6H H i 7.88 (s) 3H H c de 7.7 8.8 (hr) 6H Proton decoupling at 8.22 -r simplified the 4.75multiplet to a double-doublet.

C H O CL, requires: C, 38.7%; H, 5.20%; CI; 45.7%; found: C, 38.9%; H,5.13%; Cl, 45.4%

EXAMPLE 4 2,7-Octadien-l-yl acetate (6.7g; 0.04 mole) was dissolved inchloroform (36 ml) containing pyridine (4 ml) and then treated withchlorine at 40 ml min for 5 7 min in the same manner as described inExample 2 except that the temperature was kept below C. The reactionsolution was diluted with chloroform 100 ml), washed with water, anddried over magnesium sulphate. The chloroform was removed under reducedpressure and the residue stripped as in Example 2. GLC analysisindicated that the product (10.8 g) contained2,3,7,8-tetrachloro-l-octyl acetate (95%).

EXAMPLE 5 C H, O Cl requires: C, 38.7%; H, 5.2%; Cl, 45.8%;

found: C, 37.2%; H, 4.7%; Cl, 46.9%;

EXAMPLE 6 2,7-Octadien-l-yl benzoate (924g; 0.4 mole) was dissolved inchloroform (270 ml) and pyridine (30ml) and then treated with chlorineat 90 ml min for 3.7h in the same manner as described in Example 2except that the temperature was kept below 5C. The reaction solution wasdiluted with chloroform (270 ml), washed with water, dilute hydrochloricacid (2x), so-

dium carbonate solution, water, and dried over magnesium sulphate.Removal of the chloroform under reduced pressure gave a dark brown oil(123g). The reaction product was decolourised by passing a solution inbenzene/hexane (1:1) down a column of activated charcoal. Removal ofbenzene/hexane from the eluate gave a pale yellow oil, which was steamstripped at C for 6h and vacuum stripped at 80C for 6h. GLC analysisindicated that the product (89g) contained 2,3,7,8-tetrachloro-l-octylbenzoate (77%).

I claim:

1. Esters of linear C alcohols of the general formula Z(CH .Z.CH.O.CO.R(Y), (I) or Z(CH .CH(Z).O.CO.R(Y), (11) wherein Z is XCH .CHX andZ is CHX.Cl-1X and X is C] or Br,

R is divalent phenylene,

.CH.O.CO. 2 Z

and

x is 1. 2. Di(2,3,7,8-tetrachloro-l-octyl) phthalate. 3. The esteraccording to claim 1, wherein R is orthophenylene.

1. ESTERS OF LINEAR C8 ALCOHOLS OF THE GENERAL FORMULAZ(CH2)3.Z1.CH2.O.CO.R(Y)X OR Z(CH2)3.CH(Z).O.CO.R(Y)X WHEREIN Z IS XCH2,CHXAND Z1 IS -CHX.CHXAND X IS CH OR BR, R IS DIVALENT PHENYLENE, Y ISZ(CH2)3.Z1.CH2.O.CO OR
 2. Di(2,3,7,8-tetrachloro-1-octyl) phthalate. 3.The ester according to claim 1, wherein R is orthophenylene.